Process of obtaining paranitranilin red, &amp;c.



FUNITED STATES PATENT oFFIoE;

EMiLE AUGUST FOURNETAUX, or MANCHESTER, ENGLAND, ASSIGNOR TO BADISOHE ANILIN &

som FABRIK, or LUDWIGSHAFENLON-THE-RHINE, GERMANY, A CORPORATION.

Specification of Letters Patent.

Patented Feb. 23, 1909.

Application filed November 29, 1907. Serial No. 404,426.

To all whom "it may concern:

Be it known that I, EMILE AUGUST FOURNEAUX, a citizen of the United States, residing at Melrose, Crumpsall, Manchester,

5 in the county of Lancaster, England, have invented new and useful Improvements in the Production of Red Shades on the Fiber,

. of which the following is a specification.

My invention relates to improvements in printing or dyeing paranitranilin red and similar colorinlg1 matters on textilefibers.

Heretofore t e only practical method with which I am acquainted of producing paramtranilin red on the fiber has been to impre ate the fiber with an alkaline betana thol solution, dry, and then rint, or pa with a diazotized aranitran in solution. Various attempts ave been made to combine the two com orients in one printmg color or solution 'u't Without tactical success. The most promising of t ese attempts consisted in the use of nitrosamin red, the'so'diu'm salt of the inactive .t'rodiazobenzol, mixed with an a kaline naphthol solution, with or without the add1t1on of ammonia salts, the colorbeing developed by exposing the printed ood's to the air, or to acid vapors, or to t e action of steam, but this process has not been applied in practice because the shade of red obtained is not sufiioiently good, the process is unreliable, and the printing or dyeing colors unstable. 1 have made an exhaustive study of thisprocess in order to ascertain the causes of these shortcomin s and to obviate'them if possible. I have ound that if a mixture of nitrosamin red and an alkaline betanaphthol solution is used the red is affected by the alkali which is freed upon its formation. A good red can be obtained if this excess of alkali is reduced by usin a solution of naphthol in soap instead 0 in alkali, or by using naphthol in a state of extremely fine division, .but the colors so prepared are not stable.- If, on the other hand, nitrosamin red is used'in connection with an "alkaline betanaphthol solution and an ammonium salt the first effect is the production of a decomposable ammonium salt of the nitrosamm red, and the red obtained is tarnished by the brown bodies formed by the decomposition of this salt.

My invention consists in the addition of suitable esters to the above mentioned mixaraniture of nitrosamin red and an alkaline betana hthol solution, for the pur ose of neutra lzing the injurious excess 0 alkali gpnerated when the reactiontakes place.

nder the term of esters I mean to 'include all or anic substances which yield acids by hydro ysis, particularly also the esters desoluble inwater, not too volatile, and which do not hydrolize so readily as to cause the premature formation of paranitranilin red in the printing color.

I prefer to carry out my invention by printlng or paddin the textile fiber with a an alkaline. betanaphthol solution, nitrosamin red and an ester, or esters, with or without the customary additions such as naphtholmonosulfonic acid F, Turkey red oil, castor oil soap, and so on. Further useful additions to this mixture are mineral alogen acids, such as dichlor-' tha t/ suitable mixture, t ickened if necessary, of

salts such as Glauber salt, which improve the stability of the printin colors, and certain metallic oxide or hy rates such as alumina hydrate or zinc oxid. If desired, however, as an alternative process the fibers may be prepared in the ordinary way with an alkaline betanaphthol solution, with .or without the customary additions mentioned above, dried, and then printed or padded with nitrosamin red (su1tably thickened if necessary) rovided an addition of the proper.

quantity 0 a suitable ester or esters be made either to the prepare'or to the nitrosamin color, or to both. In this case the solution of nitrosamin red can be made morestable by the addition of suitable mineral salts as mentioned above, or by the addition of small quantities of alkalies, which must be taken into account in determining the amount of acid ether to be used. The advantage of this latter process over the ordina process of pre aring the cloth with an alka ine betanapht 101 solution and printing with a solution of the active paranitrodiazobenzol, is

based on the fact thatthe inactive diazo compound nitrosamin red is far more stable than the active compound, hence it works *5 better in the printing machine. In either case the red is developed by letting the goods lie for a sufiicient length of time after drying, or by a short steaming, preferably after the red has been partly fastened by allowing the goods to lie.

The printing or padding colors may be used for the production of the wellknown resist or discharge styles. Thus they may be resisted by colors containing sulfites or organic acids or suitable acid salts, or they may be used for resisting or discharging other colors; For. instance, a color of the type of Example 1 given below printed with the addition of zinc white or other suitable alkaline bodies and padded with anilin black after the red has been partly developed by lying, then aged, washed and soaped, produces a fast red resist under anihn black; with the addition of suitable metallic chromates a color of the type of Example 1 printed on indigo dyed cloth and developed by allowing the goods to lie with or without a short steaming to follow, then assed through the customary cutting batl i roduces a fast red discharge on indig'o lue ground. Such applications may of course be multiplied and I do not mean to restrict myself to the above, which are merely given as examples.

My invention applies to the use of nitrosamin red, i. e. paranitrophenyl nitrosamin, and also of other nitrosamins which are suitable for combining with betanaphthol to form dyestuffs on the fiber, such for instance 40 as the nitrosamins described in the specifications of Letters Patent Nos. 531,974, 531,975, 531,976, and 531,977.

The following examples will serve to illustrate further the nature of my invention and the method of carrying it into practical effect, but the invention is not confined to these examples. The parts are by weight.

Exam le 1: Twenty-five (25) parts betanaphtho andtwenty-five (25) parts castor oil soap containing about sixty (60) per cent. fatty acids are dissolved in fifty (50) parts caustic soda thirty-six (36) degrees Twaddell and one hundred and twenty (120) parts water. This solution is stirred into five hundred and fifty (550) parts of a gum tragacanth solution in which sixty (6 0) parts of Glauber salt have been previously dissolved. Before use add fifteen (15) parts chlorethylalcohol and fifteen (15) parts neutral acetin containing forty-two (42) per cent. combined acetic acid and one hundred and twenty-five (125) parts of a twenty-five (25) per cent. nitrosamin red paste. This color is printed on white cloth and the goods are allowed to lie twenty-four (24) hours. They can then four (94) either be aged or not as the conditions may require.

Exam le 2: Twenty-five (25) parts betanaphtho and thirty (30) parts of castor oil soap containing about sixty (60) per cent. fatty acids are dissolved in fifty (50) parts caustic soda thirty-six (36) degrees Twaddell and one hundred and twenty (120) arts water. On the other hand one hundre and twenty-five (125) parts nitrosamin red, twenty-five (25) per cent. paste, are dissolved in nine hundred (900) parts water, the two solutions are mixed and fifteen (15) arts chlorethylalcohol and fifteen (15) parts'neutral acetin containing forty-two (42) per cent. combined acetic acid added, and the whole made up to one thousand two hundred and fifty (1,250) parts by addition of water. Unprepared fiber is slo -padded with this solution and dried, and t e red developed by allowing the goods to lie twenty-four (24) hours. They can then be aged or not as may be required.

Example 3: Three (3) parts betanaphthol and four ('4) parts castor oil soap containing about sixty (60) per cent. fatty acids are dis solved in six (6) parts caustic soda thirty-six (36) degrees Twaddell and the required amount of hot water, the solution is then made up to one hundred and twenty (120) parts and one (1) part of chlorethylalcohol added. This solution is used for slop-padding the white fiber, which is then printed with the following color. One hundred and twenty-five (125) parts of nitrosamin red twenty-five (25) per cent. paste are stirred into seven hundred (700) parts of a tragacanth solution in which fifty (50) parts Glauber salt have been previously dissolved, and to which fifteen (15) parts of spirits of turpentine are added. Add to this a solution of twenty-four (24) parts urethane in ninetyarts water. The goods are allowed to 'e for twenty-four (24) hours, and can then either' be aged or not as the con- 11o ditions may require.

Now what I claim is:

1. The production of paranitranilin red and similar coloring matters on the fiber by applying to the fiber an alkaline betanapht 01 solution and a nitrosamin com ound and neutralizing the injurious excess 0 alkali generated with an ester. t

2. The production of paranitranilin red and similar coloring matters by a plying to the fiber an alkaline betanaphtho solution,

a nitrosamin compound and a suitable ester and then developing substantially as described.

3. The production of paranitranilin red and similar coloring matters on the fiber by preparin the fiber with an alkaline betanaphtho solution to which a suitable ester has been added, then drying, then printing or padding with a nitrosamin compound to which a suitable acid ether has been added and then developing substantially as described.

' able ester has been added, then drying, then printing or padding with nitrosamin red to which a suitable acid ether has been added and then developing substantially as described.

6. The production of paranitranilin red by applying to the fiber an alkaline betanapht 01 solution, nitrosamin red and acetinand then developing substantially as described.

7' The production of paranitranilin red on the fiber by re arin the fiber with an alkaline betana t 01 so ution to which acetin hasbeen a ded, then drying, then printing or padding with nitrosamin red to which acetin has been added and then developing substantially as described.

The production of paranitranilin red by applying 'to the fiber an alkaline betanaphthol solution, nitrosamin red and acetin and then developing by (1 ingand steaming substantially as described.

9. The production of paranitranilin red on the fiber by repa the fiber with an alkaline betana lithol so ution to which acetin has been a ded, then drying, then printing or padding with nitrosamin red to which acetin has been added and then developing by drying and steaming substantially as described.

In testimony whereof I have hereunto set my hand in the presence of two subscribing witnesses.

EMILE AUGUST FOURNEAUX.

Witnesses:

S. W. GILLETT, HERBERT ROWLAND ABBEY. 

